JP3840518B2 - Immobilizing material for gaseous hydrocarbons, its use and method for solidifying hydrocarbons - Google Patents
Immobilizing material for gaseous hydrocarbons, its use and method for solidifying hydrocarbons Download PDFInfo
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- 229930195733 hydrocarbon Natural products 0.000 title claims description 80
- 150000002430 hydrocarbons Chemical class 0.000 title claims description 80
- 239000000463 material Substances 0.000 title claims description 41
- 230000003100 immobilizing effect Effects 0.000 title claims description 20
- 238000000034 method Methods 0.000 title claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 51
- 239000013078 crystal Substances 0.000 claims description 40
- 239000004215 Carbon black (E152) Substances 0.000 claims description 38
- -1 lithium carboxylate Chemical class 0.000 claims description 38
- 239000000835 fiber Substances 0.000 claims description 29
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 28
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 26
- 229910052744 lithium Inorganic materials 0.000 claims description 19
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 17
- 239000004202 carbamide Substances 0.000 claims description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- 229910052708 sodium Inorganic materials 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 10
- 229910052700 potassium Inorganic materials 0.000 claims description 9
- 239000011591 potassium Substances 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 8
- 238000007711 solidification Methods 0.000 claims description 7
- 230000008023 solidification Effects 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 3
- 238000010583 slow cooling Methods 0.000 claims description 3
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims 1
- 239000007789 gas Substances 0.000 description 19
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 17
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 15
- 238000003756 stirring Methods 0.000 description 14
- 239000007788 liquid Substances 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 8
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- 239000007864 aqueous solution Substances 0.000 description 7
- 239000005639 Lauric acid Substances 0.000 description 6
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000004880 explosion Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
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- 238000002425 crystallisation Methods 0.000 description 2
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- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- AZEPWULHRMVZQR-UHFFFAOYSA-M lithium;dodecanoate Chemical compound [Li+].CCCCCCCCCCCC([O-])=O AZEPWULHRMVZQR-UHFFFAOYSA-M 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
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- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
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- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
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Description
本発明は、気体である炭化水素に対する固定化材及びその製造方法、並びに、気体である炭化水素を固形化する方法に関する。詳しくは、カルボン酸リチウムの長繊維状の結晶を用いた、気体である炭化水素に対する固定化材及びその製造方法、並びに、その固定化材を用いて気体である炭化水素を固形化する方法に関する。 The present invention relates to an immobilizing material for gaseous hydrocarbons, a method for producing the same, and a method for solidifying gaseous hydrocarbons. Specifically, the present invention relates to an immobilization material for gaseous hydrocarbons using a long-fiber crystal of lithium carboxylate, a method for producing the same, and a method for solidifying gaseous hydrocarbons using the immobilization material. .
石油化学、天然ガス工業の規模が年々拡大され、有機化合物が大量生産、大量消費されるようになったことに伴い、各種化学工場、石油化学コンビナートやタンカーの事故による河川、湖沼、海洋等の汚染、火災、爆発事故など、人類、生物の生存をも脅かす公害や事故が世界的に頻発しており、とりわけ石油化学物質をはじめとする気体状態の炭化水素の安全な取り扱い、輸送、備蓄時の適切な処理が大きな問題となっている。これらの爆発、火災、漏出事故に対する根本的な対策の１つは、各種化学工場、石油化学コンビナートやタンカーで取り扱う、大量の気体状態の炭化水素、それらの混合物を、安全な固形状に変化させ、必要に応じて、元の気体状態に戻すことである。安全で取扱が容易な固形状にすることによって、多くの事故を未然に防ぎ、且つ、巨大で、多くの危険性を有する貯蔵施設、パイプライン、運搬形態、冷凍、保温施設等を、大幅に変更することが可能になるものと思われる。また、化学工場の生産設備等から排出される排気ガス等に含まれる炭化水素、及び、液体である炭化水素から気化した蒸気を選択的に吸着、除去することは、資源の有効利用、大気汚染防止、爆発等の危険防止の観点からも、極めて重要なことである。 As the scale of the petrochemical and natural gas industries has been expanded year by year, and the mass production and consumption of organic compounds has increased, various chemical factories, rivers, lakes, oceans, etc. caused by accidents of petrochemical complexes and tankers Pollution, fires, explosion accidents, and other pollution and accidents that threaten the survival of human beings and organisms are occurring frequently around the world, especially during the safe handling, transportation, and storage of petrochemicals and other gaseous hydrocarbons. Appropriate processing is a big problem. One of the fundamental countermeasures against these explosions, fires, and leakage accidents is to convert a large amount of gaseous hydrocarbons and their mixtures that are handled in various chemical factories, petrochemical complexes and tankers into safe solid forms. If necessary, return to the original gaseous state. By making it safe and easy to handle, many accidents can be prevented, and huge, dangerous storage facilities, pipelines, modes of transportation, refrigeration, heat insulation facilities, etc. It seems possible to change. In addition, selective adsorption and removal of hydrocarbons contained in exhaust gas discharged from production facilities of chemical factories and vapors vaporized from liquid hydrocarbons is an effective use of resources and air pollution. This is also extremely important from the viewpoint of prevention and explosion prevention.
このような諸点を考慮すると、各種化学工場、石油化学コンビナートやタンカーで取り扱われている多種多様な気体状態の炭化水素、低沸点液体炭化水素、排ガス中に含まれる炭化水素等を容易に固形化して安全な形態に変化させ、必要に応じて元の炭化水素に戻す方法の開発が望まれる。何らかの化学反応を起こさせ、気体又は液体状態の炭化水素を他の安全な物質に変えてしまうことは、何ら解決にはならず、化学反応を伴う方法は避けなければならない。
このように考えると、物理化学的な手段を用いて、そのままの形で固形化する方法が、最も好ましいと考えられる。
Considering these points, various hydrocarbons handled in various chemical factories, petrochemical complexes and tankers, low-boiling liquid hydrocarbons, hydrocarbons contained in exhaust gas, etc. are easily solidified. Therefore, it is desired to develop a method for changing to a safe form and returning to the original hydrocarbon if necessary. Making any chemical reaction and changing the hydrocarbon in the gas or liquid state into another safe substance cannot be solved at all, and a method involving a chemical reaction must be avoided.
In view of this, it is considered that the method of solidifying as it is using the physicochemical means is most preferable.
気体である炭化水素に対する固定化材が備えるべき条件としては、ｉ）工場内の反応装置を傷めることなく、容易に気体である炭化水素を固形化することが出来、また、固形化された集合体から、容易に元の炭化水素を回収でき、更に、回収された固定化材のリサイクル使用が可能であること、ii）化学的に比較的安定であること、iii）大量に使用されることが想定されるので、安全かつ無害な物質であり、万一、反応装置外への漏出が発生し回収が困難となっても、それ自体が環境中に棲む生物及び環境に対し悪影響を及ぼす危険が少ないこと、などが挙げられる。 The conditions for the immobilization material for gaseous hydrocarbons are as follows: i) The gaseous hydrocarbons can be easily solidified without damaging the reactor in the factory. The original hydrocarbon can be easily recovered from the body, and the recovered immobilization material can be recycled. Ii) It is chemically stable. Iii) It is used in large quantities. Therefore, it is a safe and harmless substance, and even if it leaks out of the reactor and becomes difficult to collect, there is a risk that it will adversely affect living organisms and the environment that are themselves in the environment. There are few things.
このような物理化学的捕集材としては、短繊維状もしくは長繊維状のカルボン酸ナトリウム及びカルボン酸カリウムが考案されている(例えば、特許文献１参照)。これらの短繊維状もしくは長繊維状のカルボン酸ナトリウム及びカルボン酸カリウムは、極めて優れた気体炭化水素捕集能を有し、多量の炭化水素を安定に捕集することが知られているが、水への溶解度が比較的大きいことから、有効な炭素鎖長や、水溶液中での有効な塩濃度が限定される等のさらなる改良の余地を残していた。また、これらの繊維は、水中に分散した形態では極めて安定にその作用を長期間保持するが、乾燥状態では、繊維状結晶から、板状結晶に、安定形態が変化し、その結果、気体である炭化水素の捕集能が大きく低下する等の場合もあった。
したがって本発明は、上記のような条件を満足する気体である炭化水素に対する固定化材を提供することを目的とする。また、本発明は、気体である炭化水素類を物理化学的方法によって効率よく固形化しうる方法を提供することを目的とする。Therefore, an object of the present invention is to provide an immobilizing material for hydrocarbons that are gases that satisfy the above-described conditions. Another object of the present invention is to provide a method capable of efficiently solidifying hydrocarbons which are gases by a physicochemical method.
本発明者らは、種々の長さのアルキル基を有する脂肪族カルボン酸リチウムの水中における合成、溶解、乳化、分散挙動について検討する過程で、これらのカルボン酸リチウムが高温では、尿素を添加することによって、完全に水に溶解すること、また、必要に応じて、塩化リチウムを添加することによって、その溶解度を調節できること、完全溶解状態から撹拌、徐冷することによって、初めて、カルボン酸リチウムは長繊維状結晶体となって析出すること、このようにして得られた長繊維状結晶は、極めて高純度の結晶として精製、乾燥して、長時間保存できること、更に、このような繊維状集合結晶体が、特に効率よく各種炭化水素を固形化することを見出した。本発明はこの知見に基づき検討を重ね、なされたものである。 In the process of examining the synthesis, dissolution, emulsification, and dispersion behavior of aliphatic lithium carboxylates having various lengths of alkyl groups in water, the present inventors add urea at high temperatures to these lithium carboxylates. The lithium carboxylate can be dissolved for the first time only by being dissolved in water completely, and if necessary, by adjusting the solubility by adding lithium chloride. Precipitate as long fibrous crystals, the long fibrous crystals obtained in this way can be purified, dried and stored for a long time as very high purity crystals, and such fibrous aggregates It has been found that the crystals solidify various hydrocarbons particularly efficiently. The present invention has been made based on this finding.
すなわち本発明は、 That is, the present invention
（１）純水中に炭素数９〜１８の脂肪族カルボン酸、水酸化リチウム、及び、尿素を溶解させた後、徐冷し、析出した炭素数９〜１８のカルボン酸リチウム長繊維結晶からなる、２０℃、０．１ＭＰａで気体である炭化水素に対する固定化材。(1) After dissolving aliphatic carboxylic acid having 9 to 18 carbon atoms, lithium hydroxide, and urea in pure water, cooling slowly, and depositing from 9 to 18 carbon carboxylate long fiber crystals having precipitated carbon An immobilizing material for hydrocarbon that is gaseous at 20 ° C. and 0.1 MPa.
（２）前記純水中に、さらに塩化リチウムを溶解させたことによって得られる、（１）項記載の固定化材。(2) The immobilization material according to (1), which is obtained by further dissolving lithium chloride in the pure water.
（３）純水中に炭素数９〜１８の脂肪族カルボン酸ナトリウムもしくはカルボン酸カリウム、及び、尿素を完全に溶解させた後、塩化リチウム水溶液を加え、徐冷し、析出した炭素数９〜１８のカルボン酸リチウム長繊維結晶からなる、２０℃、０．１ＭＰａで気体である炭化水素に対する固定化材。(3) After completely dissolving an aliphatic sodium carboxylate or potassium carboxylate having 9 to 18 carbon atoms and urea in pure water, an aqueous lithium chloride solution is added, and the mixture is slowly cooled, and the precipitated 9 to 9 carbon atoms are precipitated. An immobilizing material for hydrocarbon which is a gas at 20 ° C. and 0.1 MPa, comprising 18 lithium carboxylate long fiber crystals.
（４）長繊維状結晶が乾燥されたものであることを特徴とする（１）〜（３）のいずれか１項に記載の固定化材。(4) The immobilization material according to any one of (1) to (3), wherein the long fibrous crystals are dried.
（５）（１）〜（４）のいずれか１項に記載の固定化材を用いて、２０℃、０．１ＭＰａで気体である炭化水素を固形化する、炭化水素の固形化方法。(5) A method for solidifying a hydrocarbon, wherein the hydrocarbon as a gas is solidified at 20 ° C. and 0.1 MPa using the immobilizing material according to any one of (1) to (4).
（６）（１）〜（４）のいずれか１項に記載の固定化材を用いて、２０℃、０．１ＭＰａで気体である炭化水素を固形化し、得られた固形状集合体を加熱して分解し、カルボン酸リチウム結晶及び気体状態の炭化水素に分離して、回収し、再利用する、炭化水素の固形化方法。(6) Using the immobilizing material according to any one of (1) to (4), the hydrocarbon that is a gas is solidified at 20 ° C. and 0.1 MPa, and the obtained solid aggregate is heated. The solidification method of hydrocarbon which decomposes | disassembles, isolate | separates into lithium carboxylate crystal | crystallization and gaseous hydrocarbon, collects, and recycles.
を提供するものである。Is to provide.
本発明の固定化材により、工場内の反応装置を傷めることなく、容易に２０℃、０．１ＭＰａで気体である炭化水素（以下、単に「気体炭化水素」ともいう）を固形化することができ、また、固形化された集合体から、容易に元の炭化水素を回収でき、更に、回収された固定化材のリサイクル使用が可能である。また、本発明の固定化材は化学的に比較的安定である。また、安全かつ無害な物質であり、万一、反応装置外への流出が発生し回収が困難となっても、それ自体が環境中に棲む生物及び環境に対し悪影響を及ぼす危険が少ない。
さらに、本発明の固定化材は、極めて優れた気体炭化水素捕集能を有し、多量の炭化水素を安定に捕集し、水中に分散した形態では極めて安定にその作用を長期間保持するのに加え、乾燥状態でも、結晶の形態が安定し、炭化水素の高い捕集能を維持することができる。
The immobilizing material of the present invention can easily solidify hydrocarbons that are gases at 20 ° C. and 0.1 MPa (hereinafter also simply referred to as “gas hydrocarbons”) without damaging the reactor in the factory. In addition, the original hydrocarbons can be easily recovered from the solidified aggregate, and further, the recovered immobilizing material can be recycled. Moreover, the immobilization material of the present invention is chemically relatively stable. In addition, it is a safe and harmless substance, and even if it flows out of the reactor and becomes difficult to recover, there is little risk of adversely affecting living organisms living in the environment and the environment.
Furthermore, the immobilizing material of the present invention has an extremely excellent gas hydrocarbon capturing ability, stably collects a large amount of hydrocarbons, and retains its action for a long period of time when dispersed in water. In addition to this, even in a dry state, the crystal form is stable, and a high capturing ability of hydrocarbons can be maintained.
本発明において、気体炭化水素の固定化材の製造に用いるカルボン酸、カルボン酸ナトリウム、又は、カルボン酸カリウムは、好ましくは直鎖状のアルキル鎖を有する構造の化合物である。カルボン酸、カルボン酸ナトリウム、又は、カルボン酸カリウムの炭素数は、９〜１８であり、好ましくは１１〜１８である。即ち、カルボン酸の場合には水酸化リチウムを加え、カルボン酸ナトリウム、カルボン酸カリウムの場合には塩化リチウムを加え、更に適量の尿素を加え、加熱することによって、純水中に完全に溶解し、撹拌、徐冷することによって結晶として析出することが出来るだけの、適度な長さのアルキル鎖長を有していることが必要である。
通常の加熱手段により上記の各成分は純水に溶解させることができるが、完全溶解のために、必要に応じて、加える塩化リチウムの濃度を著しく濃くしたり、１００℃以上に加熱温度を上げたり、尿素濃度を著しく高くすることなどを適宜行うことができる。
In the present invention, the carboxylic acid, sodium carboxylate or potassium carboxylate used for the production of the gaseous hydrocarbon immobilization material is preferably a compound having a structure having a linear alkyl chain. Carbon number of carboxylic acid, sodium carboxylate, or potassium carboxylate is 9-18, Preferably it is 11-18. That is, in the case of carboxylic acid, lithium hydroxide is added. In the case of sodium carboxylate and potassium carboxylate, lithium chloride is added. Further, an appropriate amount of urea is added and heated to completely dissolve in pure water. It is necessary to have an alkyl chain length of an appropriate length that can be precipitated as crystals by stirring and slow cooling.
The above-mentioned components can be dissolved in pure water by ordinary heating means. However, for complete dissolution, the concentration of added lithium chloride is remarkably increased or the heating temperature is raised to 100 ° C. or higher as necessary. It is possible to appropriately increase the urea concentration.
本発明において、長繊維状に結晶を析出する際のカルボン酸：水のモル比は、好ましくは０.５：１０００〜５：１０００、更に好ましくは０.５：１０００〜２：１０００である。
また、水酸化リチウムはカルボン酸に対し、好ましくは９０モル％〜１１０モル％、さらに好ましくは、９５モル%〜１０５モル%の範囲の濃度である。
In the present invention, the molar ratio of carboxylic acid: water at the time of depositing crystals in the form of long fibers is preferably 0.5: 1000 to 5: 1000, more preferably 0.5: 1000 to 2: 1000.
Lithium hydroxide is preferably 90 to 110 mol%, more preferably 95 to 105 mol% of the carboxylic acid.
尿素の添加量は、用いるカルボン酸の種類によって変化するが、通常、カルボン酸に対して、好ましくは１〜１６倍、さらに好ましくは２〜８倍のモル比とするものである。
しかしながら、例えば、ステアリン酸を用いた場合には、８〜１６倍のモル比の尿素を加えることが好ましい。
The amount of urea to be added varies depending on the type of carboxylic acid to be used, but is usually 1 to 16 times, more preferably 2 to 8 times the molar ratio of the carboxylic acid.
However, for example, when stearic acid is used, it is preferable to add urea in a molar ratio of 8 to 16 times.
炭素原子数９から１１のカルボン酸を用いる場合には、カルボン酸リチウムの水への溶解を抑制し、析出量を増大させるために、更に、塩化リチウムを水中に、カルボン酸に対して０．５から１モルの比率で添加し、溶解させることが好ましい。
また、炭素原子数１２のカルボン酸であるドデカン酸（ラウリン酸）を用いる場合には、塩化リチウムは無添加とするか、あるいは０．５モル程度までの量を添加することが好ましい。炭素原子数１３以上のカルボン酸を用いる場合には、塩化リチウムは無添加とすることが好ましい。
また、本発明において純水とは、海水ではない水のことを言い、塩分が実質的に含まれない水が好ましい。
In the case of using a carboxylic acid having 9 to 11 carbon atoms, in order to suppress the dissolution of lithium carboxylate in water and increase the amount of precipitation, lithium chloride is further added to the carboxylic acid in water in an amount of 0. It is preferable to add and dissolve at a ratio of 5 to 1 mole.
In addition, when dodecanoic acid (lauric acid), which is a carboxylic acid having 12 carbon atoms, is used, it is preferable that lithium chloride is not added or an amount up to about 0.5 mol is added. When a carboxylic acid having 13 or more carbon atoms is used, it is preferable to add no lithium chloride.
In the present invention, pure water means water that is not seawater, and water that is substantially free of salt is preferred.
長繊維状にカルボン酸リチウムを析出させるには、析出させる前に、カルボン酸を一旦完全に水に溶解させることが必要である。しかし、例えば、ラウリン酸リチウムＣ１１Ｈ２３ＣＯＯＬｉを析出させる場合、そのままではウラリン酸は溶解させることが非常に困難である。少量のラウリン酸（例えば、水１０００モルに対し、ウラリン酸１モル）を加えることによってようやく水温９８〜１００℃の熱湯に溶解するが、等モルの水酸化リチウムのみを加えた水溶液では、徐冷後、燐片状、板状、或いは棒状の結晶のみが析出する。ラウリン酸とＬｉＯＨ／Ｈ２Ｏのモル比をわずかに変化させ、更に２モル程度の尿素を加えることによって、長繊維状の結晶が水中に大量に析出する。このようにして得られた結晶が確かにＬｉ塩であることは、例えば通常のフーリエ変換赤外分光法（ＦＴＩＲ）により確認することができる。同様にして、Ｃ９からＣ１８までの各種カルボン酸の場合にも、カルボン酸、水酸化ナトリウム、水、尿素添加量を調節することによって、長鎖状リチウム塩を水中で作ることが可能である。 In order to deposit lithium carboxylate in the form of long fibers, it is necessary to completely dissolve the carboxylic acid in water before the precipitation. However, for example, when lithium laurate C 11 H 23 COOLi is deposited, it is very difficult to dissolve uraric acid as it is. A small amount of lauric acid (for example, 1 mol of uraric acid per 1000 mol of water) is finally dissolved in hot water at a water temperature of 98-100 ° C., but in an aqueous solution containing only equimolar lithium hydroxide, it is slowly cooled. Thereafter, only flake-like, plate-like, or rod-like crystals are deposited. By slightly changing the molar ratio of lauric acid and LiOH / H 2 O, and adding about 2 moles of urea, a large amount of long fiber crystals are precipitated in water. It can be confirmed, for example, by ordinary Fourier transform infrared spectroscopy (FTIR) that the crystals thus obtained are indeed Li salts. Similarly, in the case of various carboxylic acids from C 9 to C 18 , a long-chain lithium salt can be produced in water by adjusting the addition amount of carboxylic acid, sodium hydroxide, water and urea. is there.
本発明において、「徐冷」とは、通常の冷却方法により、加熱された状態から室温までゆっくりと温度を下げることを言い、好ましくは１時間当たり、５〜５０℃冷却するものである。
また、本発明に用いられる長繊維状の結晶の１本の太さは好ましくは５μｍ以下、長さは好ましくは１００〜２０００μｍ、より好ましくは５００〜２０００μｍである。また、１本の長繊維状の結晶は、更に細い多数の繊維状の結晶より構成されている。
また、撹拌は、それぞれ従来用いられている方法のいずれかを適宜選択して行うことができる。
In the present invention, “slow cooling” refers to slowly lowering the temperature from a heated state to room temperature by a normal cooling method, and preferably cooling at 5 to 50 ° C. per hour.
Moreover, the thickness of one long fiber crystal used in the present invention is preferably 5 μm or less, and the length is preferably 100 to 2000 μm, more preferably 500 to 2000 μm. One long fiber crystal is composed of a number of finer fiber crystals.
Moreover, stirring can be performed by appropriately selecting any one of the methods conventionally used.
本発明の固定化材製造の一つの実施態様は、以下の１）の通りである。
１）純水中にカルボン酸および尿素を溶解、懸濁して加熱、攪拌しながら、カルボン酸に対しておよそ等モル量の水酸化リチウムをゆっくりと滴下する。アルキル鎖長の短いカルボン酸の場合には、更に、塩化リチウムを加える。滴下完了後、攪拌を続けながら、室温までゆっくりと温度を下げる。更に、必要に応じて、室温で攪拌を続け、また、攪拌を停止して、室温で長時間静置する。高純度の結晶は、炭素原子数１６までのカルボン酸リチウムの場合には一般に、その結晶形態に関わらず、反応容器内に存在する水全体に一様に分散する形で得られる。長繊維状の結晶が得られる場合には、総ての水を抱え込んで、全体が白色のゲル状を呈することもある。また、炭素原子数１７以上のカルボン酸リチウムの場合にも、大半の水に分散する形で、水の上部に一様に析出する。
得られた結晶は、吸引ロートで濾過し、更に純水で洗浄して、水に溶解している尿素、場合によっては塩化リチウム、および、微量に残存している可能性のあるカルボン酸、水酸化リチウムを、完全に除去する。必要に応じて、更に、新たな純水中に懸濁、攪拌し、吸引濾過、洗浄を繰り返す。最後に真空乾燥を行い、固定化材を得る。
One embodiment of the production of the immobilizing material of the present invention is as follows 1).
1) Dissolve and suspend carboxylic acid and urea in pure water, slowly add dropwise about equimolar amount of lithium hydroxide to carboxylic acid while heating and stirring. In the case of a carboxylic acid having a short alkyl chain length, lithium chloride is further added. After completion of dripping, the temperature is slowly lowered to room temperature while continuing stirring. Further, if necessary, stirring is continued at room temperature, and stirring is stopped, and the mixture is allowed to stand at room temperature for a long time. In the case of lithium carboxylate having up to 16 carbon atoms, high-purity crystals are generally obtained in a form that is uniformly dispersed throughout the water present in the reaction vessel, regardless of the crystal form. When long fiber-like crystals are obtained, all the water is held and the whole may form a white gel. Also, in the case of lithium carboxylate having 17 or more carbon atoms, it is uniformly deposited on the top of the water in a form that is dispersed in most of the water.
The obtained crystals are filtered with a suction funnel, washed with pure water, urea dissolved in water, in some cases lithium chloride, and carboxylic acid that may remain in trace amounts, water Lithium oxide is completely removed. If necessary, it is suspended and stirred in fresh pure water, and suction filtration and washing are repeated. Finally, vacuum drying is performed to obtain an immobilization material.
本発明の固定化材製造の別の実施態様は、以下の２）の通りである。
２）純水中にカルボン酸ナトリウムもしくはカルボン酸カリウムおよび尿素を溶解、懸濁して加熱、攪拌しながら、カルボン酸ナトリウムもしくはカルボン酸カリウムに対して過剰量の塩化リチウムを添加する。攪拌を続けながら、室温までゆっくりと温度を下げる。更に、必要に応じて、室温で攪拌を続け、また、攪拌を停止して、室温で長時間静置する。高純度の結晶は、一般に、その結晶形態に関わらず、反応容器内に存在する水全体に一様に分散する形で得られる。長繊維状の結晶が得られる場合には、総ての水を抱え込んで、全体が白色のゲル状を呈することもある。以下、得られた結晶を上記１）と同様に処理して固定化材を得る。
Another embodiment of the production of the immobilization material of the present invention is as follows 2).
2) Dissolve and suspend sodium carboxylate or potassium carboxylate and urea in pure water, add an excess amount of lithium chloride to sodium carboxylate or potassium carboxylate while heating and stirring. While continuing to stir, slowly lower the temperature to room temperature. Further, if necessary, stirring is continued at room temperature, and stirring is stopped, and the mixture is allowed to stand at room temperature for a long time. High-purity crystals are generally obtained in a form that is uniformly dispersed throughout the water present in the reaction vessel, regardless of the crystal form. When long fiber-like crystals are obtained, all the water is held and the whole may form a white gel. Thereafter, the obtained crystal is treated in the same manner as in 1) to obtain an immobilizing material.
本発明に係るカルボン酸リチウム長繊維は、カルボン酸ナトリウム長繊維に比べ疎水性が大きいものとなる。また、析出された長繊維状の結晶は安定なもので、水から取り出して乾燥させても、長繊維構造を保っている。 The lithium carboxylate long fiber according to the present invention has higher hydrophobicity than the sodium carboxylate long fiber. The precipitated long fiber crystals are stable and maintain a long fiber structure even when taken out from water and dried.
本発明の固定化材は、気体炭化水素を導入して緩やかに振蕩するだけで、選択的に気化炭化水素を吸着する。カルボン酸リチウム長繊維に対して気化炭化水素の割合が過剰でない範囲では、水の存在下で実質的に気化炭化水素を全て吸着し、水上に浮遊する。気体炭化水素を吸着した後の複合体は、気体炭化水素の割合が小さいときには微粒子状複合体として、気体炭化水素の質量比がカルボン酸リチウム長繊維の数倍に達してからは、全体として球状の塊、ないし、丸みをおびた繊維塊として水上に浮遊する。これは容易に水中からすくい上げることができる。 The immobilization material of the present invention selectively adsorbs vaporized hydrocarbons simply by introducing gaseous hydrocarbons and gently shaking them. In the range where the ratio of the vaporized hydrocarbon to the lithium carboxylate long fiber is not excessive, all the vaporized hydrocarbon is adsorbed in the presence of water and floats on the water. The composite after adsorbing gaseous hydrocarbons is a fine-grained composite when the proportion of gaseous hydrocarbons is small. After the mass ratio of gaseous hydrocarbons reaches several times that of lithium carboxylate long fibers, the composite is spherical as a whole. Float on the water as a lump or rounded fiber lump. This can easily be scooped out of the water.
本発明の固定化材が固形化しうる、２０℃、０．１ＭＰａで気体の炭化水素としては、例えば、ｎ−ブタン、イソブタン、１−ブテン、シス−２−ブテン、トランス−２−ブテン、１，３−ブタジエン、プロパン、プロピレンなどが挙げられる。
また、本発明の固定化材は、化学工場の生産設備等から排出される排気ガス等に含まれた状態、或いは、液体である炭化水素から気化した状態であっても、特別な処理すること無しに炭化水素もそのまま固形化することができる。
Examples of hydrocarbons that are solid at 20 ° C. and 0.1 MPa that can solidify the fixing material of the present invention include n-butane, isobutane, 1-butene, cis-2-butene, trans-2-butene, 1 , 3-butadiene, propane, propylene and the like.
In addition, the immobilizing material of the present invention should be specially treated even if it is contained in exhaust gas discharged from production facilities of a chemical factory or the like, or is vaporized from liquid hydrocarbons. The hydrocarbon can also be solidified as it is.
また、本発明で、気体炭化水素の吸着、固形化を助けるために液体状態の炭化水素を若干添加してよい。用いられる液体状態の炭化水素としては、例えば、ｎ−ペンタンからｎ−ヘキサデカンまでの、２０℃、０．１ＭＰａで液体の全てのｎ−パラフィン、分岐状パラフィン、オレフィン、シクロヘキサンなどの脂環式パラフィン、ベンゼン、トルエン、キシレンなどの芳香族炭化水素、軽油、灯油、流動パラフィンなどの混合炭化水素が挙げられるが、固形化後の取り扱い、分解、回収のし易さなどを考慮すれば、不安定なオレフィン、混合炭化水素を敢えて用いる必要はなく、比較的単純で安定な構造の、パラフィン系炭化水素、脂環式パラフィン、芳香族炭化水素を用いればよい。 In the present invention, a small amount of liquid hydrocarbon may be added to assist the adsorption and solidification of gaseous hydrocarbons. Examples of the liquid hydrocarbon used include alicyclic paraffins such as all n-paraffins, branched paraffins, olefins, cyclohexanes, etc., which are liquid at 20 ° C. and 0.1 MPa from n-pentane to n-hexadecane. , Aromatic hydrocarbons such as benzene, toluene, and xylene, and mixed hydrocarbons such as light oil, kerosene, and liquid paraffin, etc., but unstable in consideration of ease of handling, decomposition, and recovery after solidification It is not necessary to dare to use such olefins and mixed hydrocarbons, and paraffinic hydrocarbons, alicyclic paraffins and aromatic hydrocarbons having a relatively simple and stable structure may be used.
固形化しようとする気体炭化水素の種類にもよるが、気体炭化水素単独の場合には、通常、本発明の固定化材１質量部に対し約１〜１００質量部の気体炭化水素を吸着させることができる。また、液体状態の炭化水素を併用する場合には、通常、本発明の固定化材１質量部に対し、約５〜５０質量部の気体炭化水素を吸着させることができるが、固形化された気体炭化水素は気体炭化水素単独の場合に比べ遥かに安定になる。
本発明の固定化材に気体炭化水素を吸着し、固形化させるには、好ましくは１分以上、気体炭化水素と固定化材を接触させればよく、緩やかに振蕩するのがさらに好ましい。
Although depending on the type of gas hydrocarbon to be solidified, in the case of the gas hydrocarbon alone, usually about 1 to 100 parts by mass of the gas hydrocarbon is adsorbed to 1 part by mass of the fixing material of the present invention. be able to. Moreover, when using together the hydrocarbon of a liquid state, about 5-50 mass parts gaseous hydrocarbon can be normally adsorb | sucked with respect to 1 mass part of fixing material of this invention, but it was solidified. Gaseous hydrocarbons are much more stable than gaseous hydrocarbons alone.
In order to adsorb and solidify the gaseous hydrocarbon on the immobilizing material of the present invention, the gaseous hydrocarbon and the immobilizing material are preferably brought into contact with each other for more than 1 minute, and it is more preferable to shake gently.
気体炭化水素のみを固形化した後の固形状集合体は、一般に、固形状集合体の蒸気圧が、大気圧よりもわずかに高いので、密閉容器に保存することが好ましい。従って、元の気体炭化水素を得るためには、常温で、大気圧下に開放し、通常の方法で気体炭化水素を回収すればよい。
気体炭化水素と液体状態の炭化水素を一緒に固形化した後の固形状集合体は、一般に、固形状集合体の蒸気圧が大気圧より低いので、密閉容器に保存することは必ずしも必要でないが、より確実に安全を確保するためには、やはり、簡易な密閉容器に保存することが好ましい。従って、この場合には、元の気体炭化水素を得るためには、約４０〜６０℃程度に加熱して、気体炭化水素を大気圧下に開放し、通常の方法で回収すればよい。
一方、上記の作業により、炭化水素から分離され、回収されたカルボン酸リチウム結晶（長繊維）は、気体である炭化水素に対する固定化材として使用しうるカルボン酸リチウム長繊維を製造するのに用いることができ、繰り返し使用することができる。
The solid aggregate after solidifying only the gaseous hydrocarbon is generally preferably stored in a sealed container because the vapor pressure of the solid aggregate is slightly higher than atmospheric pressure. Therefore, in order to obtain the original gaseous hydrocarbon, it is only necessary to open it at room temperature and atmospheric pressure and recover the gaseous hydrocarbon by a normal method.
The solid aggregate obtained after solidifying together the gaseous hydrocarbon and the hydrocarbon in liquid state is generally not necessarily stored in a sealed container because the vapor pressure of the solid aggregate is lower than atmospheric pressure. In order to ensure safety more reliably, it is still preferable to store in a simple sealed container. Therefore, in this case, in order to obtain the original gaseous hydrocarbon, it may be heated to about 40 to 60 ° C., the gaseous hydrocarbon is released under atmospheric pressure, and recovered by a normal method.
On the other hand, the lithium carboxylate crystals (long fibers) separated and recovered from the hydrocarbons by the above-described operation are used to produce lithium carboxylate long fibers that can be used as an immobilizing material for hydrocarbons that are gases. Can be used repeatedly.
ラウリン酸（n-ドデカン酸、n-C11H23COOH）8.01g（0.04モル）、尿素（(NH2)2CO）9.61g（0.16モル）、純水330gを、容量500mlのパイレックス（登録商標）製4つ口フラスコに入れ、オイルバスで加熱し（バス温度116℃、フラスコ内の水溶液の温度95℃）、ステンレス製撹拌羽根を用いて250rpmで撹拌しながら、水酸化リチウム１水和物（LiOH・H2O）1.68g（0.04モル）を30gの純水に溶かした水溶液をゆっくりとおよそ30分かけて滴下した。滴下終了後の純水の量は360g（20モル）になる。水酸化リチウムの滴下と共に、ラウリン酸は水に完全に溶解し、泡が大量に発生し、水溶液は無色透明に変化した。この間、液温は次第に上昇し、100℃に達し、一定となった。100℃に保ったまま更に撹拌を継続し、熟成を行った。この時点でラウリン酸リチウムが定量的に合成され、完全に水に溶解しているものと思われる。泡の発生量は次第に減少したが、無色透明の水溶液の状態は何等変化しなかった。2時間後ヒーターの電源を切り、撹拌速度を6rpmにして、ゆっくりと室温まで冷却した。冷却開始後30分、83℃になったところで結晶の析出が始まり、80℃で、ほぼ全量が析出した。長繊維状に結晶が互いに絡み合って、反応容器中の水全体を抱え込み、全体が均一の白色ゲル状を呈した。図１は、得られた長繊維状の結晶の光学顕微鏡写真を示す。長繊維は、単一の結晶ではなく、極めて細い短繊維が集合して、長く連なった構造をしていた。吸引濾過によって長繊維状の結晶と水溶液は用意に分離できた。結晶を更に純水で洗浄し、濾液を分離して、微量の残存ラウリン酸、水酸化リチウム、尿素を分離、除去し、真空乾燥を行って、固定化材を作成した。このように真空乾燥を行った後も、数ヶ月以上に渡って、この固定化材は、室温で安定に保たれることを確認した。元素分析の結果、約97.6%がカルボン酸リチウムであり、及び、残りの2.4%は尿素であることを確認した。また、赤外分光測定により、原料物質であるラウリン酸が残存していないことも確かめられた。
この固定化材１００ｍｇと１８ｇの純水が入った、内容量６０ｍｌの耐圧ガラス容器を−３０℃に冷却した。その容器にガスボンベからｎ−ブテン３００ｍｇを加え、密栓後、室温に戻し、軽く振とうしたところ、直ちにｎ−ブテンの固形化が確認された。
Pyrex (registered trademark) with a volume of 500 ml of lauric acid (n-dodecanoic acid, nC 11 H 23 COOH) 8.01 g (0.04 mol), urea ((NH 2 ) 2 CO) 9.61 g (0.16 mol), 330 g of pure water Place in a four-necked flask, heat in an oil bath (bath temperature 116 ° C., temperature of aqueous solution in the flask 95 ° C.), and stir at 250 rpm using a stainless steel stirring blade. An aqueous solution obtained by dissolving 1.68 g (0.04 mol) of LiOH.H 2 O in 30 g of pure water was slowly added dropwise over about 30 minutes. The amount of pure water after dropping is 360 g (20 mol). Along with the dropwise addition of lithium hydroxide, lauric acid was completely dissolved in water, a large amount of foam was generated, and the aqueous solution turned colorless and transparent. During this time, the liquid temperature gradually increased, reached 100 ° C., and became constant. Stirring was continued while maintaining the temperature at 100 ° C., and aging was performed. At this point, lithium laurate is synthesized quantitatively and appears to be completely dissolved in water. The amount of bubbles generated gradually decreased, but the state of the colorless and transparent aqueous solution did not change at all. After 2 hours, the heater was turned off, the stirring speed was 6 rpm, and the mixture was slowly cooled to room temperature. Crystallization started when the temperature reached 83 ° C. for 30 minutes after the start of cooling, and almost the entire amount was precipitated at 80 ° C. Crystals were entangled with each other in the form of long fibers, and the entire water in the reaction vessel was held, and the whole exhibited a uniform white gel. FIG. 1 shows an optical micrograph of the obtained long fibrous crystal. Long fibers were not single crystals, but had a structure in which extremely thin short fibers were assembled and long continuous. The long fiber crystals and the aqueous solution could be easily separated by suction filtration. The crystals were further washed with pure water, the filtrate was separated, and trace amounts of residual lauric acid, lithium hydroxide, and urea were separated and removed, followed by vacuum drying to prepare an immobilizing material. It was confirmed that the immobilizing material was kept stable at room temperature for several months or more after vacuum drying. As a result of elemental analysis, it was confirmed that about 97.6% was lithium carboxylate and the remaining 2.4% was urea. Further, it was confirmed by infrared spectroscopy that no lauric acid as a raw material remained.
A pressure-resistant glass container having an internal volume of 60 ml and containing 100 mg of this fixing material and 18 g of pure water was cooled to -30 ° C. To the container, 300 mg of n-butene was added from a gas cylinder, sealed, returned to room temperature, and shaken lightly. As a result, solidification of n-butene was immediately confirmed.
ｎ−ブテンに代えて、ｎ−ブタン、１，３−ブタジエン、トランス−２−ブテン、プロピレン、又は、プロパンを用いた以外は、実施例１と同様に固形化を行ったところ、気体であるそれぞれの炭化水素が固形化されたことが確認された。 Instead of n-butene, except that n-butane , 1,3-butadiene, trans-2-butene, propylene, or propane was used, solidification was performed in the same manner as in Example 1 to find a gas. It was confirmed that each hydrocarbon was solidified.
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